CN1179437C - Positive plate active material, method for producing same, and secondary cell - Google Patents

Positive plate active material, method for producing same, and secondary cell Download PDF

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CN1179437C
CN1179437C CNB008099553A CN00809955A CN1179437C CN 1179437 C CN1179437 C CN 1179437C CN B008099553 A CNB008099553 A CN B008099553A CN 00809955 A CN00809955 A CN 00809955A CN 1179437 C CN1179437 C CN 1179437C
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active material
lithium ion
ion secondary
secondary battery
oxide
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CN1360739A (en
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野田孝男
彦
白川彰彦
昭
J·加泽
善
山内庆昭
小野文善
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Resonac Holdings Corp
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Showa Denko KK
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A positive plate active material for lithium ion secondary cells mainly containing an Li-Mn composite oxide particles having a spinel structure wherein the average of the porosity (A/B) x 100 (%) (1) (where A is the total cross sectional area of the pores included in a cross section of one secondary particle, and B is the cross sectional area of one secondary particle) of the particles is 15% or less, the tap density is 1.9 g/ml or more, the crystallite size is 400-960 A, and the lattice constant is 8.240 A or less. A method for producing the positive plate active material and a lithium ion secondary cell comprising the positive plate active material are also disclosed. The particles of the positive plate active material are dense and spherical. The packability of the particles in an electrode is excellent. The initial capacity and capacity maintenance factor of the secondary cell are high even in a high-temperature environment.

Description

Positive active material, its preparation method and secondary cell
Technical field
The present invention relates to positive electrode active material for lithium ion secondary battery, its preparation method and used the lithium rechargeable battery of this positive active material.
Background technology
As positive electrode active material for lithium ion secondary battery, the good and resourceful complex Li-Mn-oxide (hereinafter referred to as the Li-Mn system complex oxide) of fail safe just attracts tremendous attention.But, the Li-Mn system complex oxide is compared with lithium cobalt composite oxide (abbreviating the Li-Co system complex oxide as), because the capacity of active material is less, comprise more space in the offspring, so offspring is light, oil absorption is bigger, the active material quality of packing in the battery that size is restricted reduces.Consequently, the capacitance problem of smaller that unit cells occurs.
As improving one's methods, proposed with 500kg/cm in recent years 2After above pressure carries out press molding to the mixture of manganese compound and lithium compound, heat treated makes its pulverizing, obtain the method (No. the 5807646th, United States Patent (USP), open the flat 9-86933 of communique number of Japan Patent) of the Li-Mn system complex oxide of tap density (making the container vibration under certain condition and the apparent density of the powder that obtains) more than 1.7g/ml.But the highest only 1.9g/ml of concrete tap density of announcement can't be satisfactory.
In addition, aforementioned communique has also disclosed the average grain diameter of the offspring that the primary particle aggegation by the Li-Mn system complex oxide forms.Though offspring utilizes the interaction between primary particle that filling is increased, being coated with in the pulp step when the modulator electrode material can not aggegation, so be not from carrying out improved method in essence.
Preparation method as Li-Mn system complex oxide with spinel structure, disclosed the preparation process of mixture of (under for example, 250 ℃～850 ℃ the temperature) sintering manganese compound and lithium compound (open the flat 9-86933 of communique number of Japan Patent) at high temperature; Be mixed into the oxide of the boron that can replace manganese in manganese compound and lithium compound again, at high temperature sintering makes, and replacing part Mn with B is the method for oxide as the Li-Mn-B of positive active material.
But, when these raw materials carry out sintering in high temperature in atmosphere or in the Oxygen Flow, the average void fraction of the offspring after the pulverizing big (more than 15%), tap density low (1.9g/ml is following), therefore, the quality of positive active material of electrode of packing into increases, and can't realize high capacity.
In addition, Japan Patent has openly disclosed for the flat 4-14752 of communique number and sneaked into titanium oxide in spinel lithium manganese oxide, with the technical scheme of the manganese series oxides behind the sintering as positive active material.If temperature is not in the scope more than 950～1000 ℃, then the reaction of titanium oxide and lithium and manganese does not generate fused solution.In addition, if the addition of titanium oxide less than 10 quality %, then can only obtain the tap density of 1.60g/ml.
The announcement of invention
The purpose of this invention is to provide that filling is good, initial capacity is high, the capacity when discharging and recharging repeatedly descends less positive electrode active material for lithium ion secondary battery, its preparation method and used the lithium rechargeable battery of this positive active material.
Present inventors have carried out conscientiously research, after the sinter that will have a Li-Mn system complex oxide of spinel structure is pulverized, add sintering and promote auxiliary agent in these sized particles, realize particle-denseization by granulation and sintering, have successfully finished aforementioned invention.
That is, the invention provides following positive electrode active material for lithium ion secondary battery, its preparation method, the electrode paste that contains this positive active material and lithium ion secondary battery anode, lithium rechargeable battery.
[1] positive electrode active material for lithium ion secondary battery, this positive active material is characterized in that using following formula to have the Li-Mn system complex oxide particle of spinel structure:
The voidage mean value of the aforementioned particles of voidage (%)=(A/B) * 100 (1) expression is below 15%, and in the formula, A represents to be included in the total sectional area in 1 hole in the offspring cross section, and B represents the sectional area of 1 offspring.
[2] further limit the positive electrode active material for lithium ion secondary battery that aforementioned [1] is put down in writing, wherein, aforementioned average void fraction is below 10%, and the average grain diameter of primary particle is 0.2～3 μ m.
[3] further limit the positive electrode active material for lithium ion secondary battery that aforementioned [1] is put down in writing, wherein, the tap density of positive active material is more than 1.9g/ml.
[4] further limit the positive electrode active material for lithium ion secondary battery that aforementioned [3] are put down in writing, wherein, the tap density of positive active material is more than 2.2g/ml.
[5] further limit the positive electrode active material for lithium ion secondary battery that aforementioned [1] is put down in writing, wherein, the crystallite size of positive active material is 400～960 dusts.
[6] further limit the positive electrode active material for lithium ion secondary battery that aforementioned [1] is put down in writing, wherein, the lattice constant of positive active material is below 8.240 dusts.
[7] further limit the positive electrode active material for lithium ion secondary battery that aforementioned [1] is put down in writing, wherein, positive active material is to have the Li-Mn system complex oxide of spinel structure, described oxide maybe can become the element of oxide by the oxide of fusion under 550 ℃～900 ℃ temperature or contain the compound of this element or with lithium or manganese solid solution or react and the oxide of fusion maybe can become the element of oxide or the compound that contains this element is formed, the active material that obtains by granulation and sintering.
[8] further limit the positive electrode active material for lithium ion secondary battery that aforementioned [7] are put down in writing, wherein, the oxide of fusion maybe can become the element of oxide or contain the compound of this element or with lithium or manganese solid solution or react and the oxide of fusion maybe can become the element of oxide or the compound that contains this element is selected from the element of Bi, B, W, Mo, Pb at least a kind or contain the compound of this element or by B under 550 ℃～900 ℃ temperature 2O 3With the compound of LiF composition or by MnF 2Compound with the LiF composition.
[9] based on the preparation method of the positive electrode active material for lithium ion secondary battery of Li-Mn system complex oxide with spinel structure, the feature of this method is, possess in the crushed material of Li-Mn system complex oxide and to add the oxide that is mixed into fusion under 550 ℃～900 ℃ temperature and maybe can become the element of oxide or contain the compound of this element or with lithium or manganese solid solution or react and the oxide of fusion maybe can become the element of oxide or contain the compound of this element, the step of carrying out granulation then with spinel structure.
[10] further limit the preparation method of positive electrode active material for lithium ion secondary battery of aforementioned [9] record, except granulation step, also possess the step of aforementioned granulation thing being carried out sintering.
[11] further limit the preparation method of positive electrode active material for lithium ion secondary battery of aforementioned [9] record, except granulation step, also possesses the step of aforementioned granulation thing being carried out sintering, during sintering, the speed with at least 100 ℃/minutes heats up till the high temperature of this temperature more than at least 100 ℃ to being higher than to shrink initial temperature from sintering, keep this temperature after 1 minute～10 minutes, make temperature reduce to the sintering initial temperature with at least 100 ℃/minutes speed again.
[12] further limit the preparation method of positive electrode active material for lithium ion secondary battery of aforementioned [11] record, carry out sintering with rotary kiln.
[13] further limit the preparation method of positive electrode active material for lithium ion secondary battery of aforementioned [10] record, when carrying out aforementioned sintering step, make at least a kind to be selected from the element of Bi, B, W, Mo, Pb or to contain the compound of this element or by B at Li-Mn system complex oxide particle surface 2O 3With the compound of LiF composition or by MnF 2The compound of forming with LiF carries out fusion and sintering.
[14] further limit the preparation method of positive electrode active material for lithium ion secondary battery of aforementioned [9] record, the average grain diameter of crushed material of Li-Mn system complex oxide with spinel structure is below 5 μ m.
[15] further limit the preparation method of positive electrode active material for lithium ion secondary battery of aforementioned [9] record, the average grain diameter of crushed material of Li-Mn system complex oxide with spinel structure is below 3 μ m.
[16] further limit the preparation method of positive electrode active material for lithium ion secondary battery of aforementioned [9] record, aforementioned granulation step adopts spray granulation, stirring-granulating method, compression comminution granulation or fluidized granulation method to carry out.
[17] further limit the preparation method of positive electrode active material for lithium ion secondary battery of aforementioned [9] record, in the aforementioned granulation step, at least a kind of organic compound that adopts the copolymer, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, hydroxypropyl cellulose, methylcellulose, cornstarch, gelatin and the lignin that are selected from acrylic resin, isobutene and maleic anhydride is as granulation aid.
[18] further limit the preparation method of positive electrode active material for lithium ion secondary battery of aforementioned [17] record, also possess in atmosphere or oxygen flow atmosphere gas in, the step of under 300 ℃～550 ℃ temperature, carrying out degreasing.
[19] positive electrode active material for lithium ion secondary battery, this active material is made by the method for each record of aforementioned [9]～[18].
[20] electrode paste wherein comprises the positive electrode active material for lithium ion secondary battery of each record of aforementioned [1]～[8].
[21] lithium ion secondary battery anode wherein comprises the positive electrode active material for lithium ion secondary battery of each or aforementioned [19] record of aforementioned [1]～[8].
[22] lithium rechargeable battery wherein possesses the lithium ion secondary battery anode that aforementioned [21] are put down in writing.
[23] further limit the lithium rechargeable battery that aforementioned [22] are put down in writing, described secondary cell is button cell, winding type battery, cylinder battery, cubic type battery or laminate type battery.
Simple declaration to accompanying drawing
Fig. 1 is the electron scanning micrograph (* 15,000 times) through one of the whole grain of granulation sintering routine positive active material (embodiment 14) of the present invention.
Fig. 2 is the particle size distribution through one of the whole grain of granulation sintering routine positive active material (embodiment 14) of the present invention.
To detailed description of the invention
Below, the present invention is described in detail.
The present invention relates to have the Li-Mn system complex oxide positive active material of spinel structure, wherein the voidage of offspring is down to below 15% than significantly reduced in the past. In addition, the invention still further relates to product in the past and compare the fabulous Li-Mn system complex oxide with spinel structure of cycle characteristics, wherein the average void fraction of offspring is below 10%.
That is, the positive active material with lithium-manganese (Li-Mn) system complex oxide of spinel structure of the present invention is by chemical formula LiMn2O 4、Li 1+xMn 2-xO 4(in the formula, x satisfies 0＜x＜0.2) or aforementioned Mn are selected from the chemical formula Li of at least a kind of element (chemical formula is abbreviated as M) replacement of chromium, cobalt, aluminium, nickel, iron, magnesium1+xMn 2-x-yM yO 4The general name of the compound of (in the formula, x satisfies 0＜x＜0.2, and y satisfies 0＜y＜0.4) expression.
Positive electrode active material for lithium ion secondary battery of the present invention is take aforementioned Li-Mn system complex oxide with spinel structure as main body, and the voidage of 1 offspring is by following formula (1):
Voidage (%)=(A/B) * 100 (1) is calculated. In the formula, A represents to be included in the total sectional area in 1 hole in the offspring cross section, and B represents the sectional area of 1 offspring. The offspring average void fraction of positive active material of the present invention is below 15%.
In addition, as aforementioned Li-Mn system complex oxide, the average void fraction of aforementioned positive active material is more preferably below 10%, and the average grain diameter of primary particle is 0.2～3 μ m.
That is, make the tap density of positive active material surpass 1.9g/ml, the average void fraction of offspring just must be below 15%. The average void fraction of offspring better is below 13%, is more preferably below 10%.
Among the preparation method of composite oxides, if generally carry out sintering shrinkage by rising sintering temperature and prolongation sintering time the average void fraction of offspring is descended as much as possible, then along with the grain growth that carries out primary particle of sintering shrinkage is accelerated, can cause the capacity dimension holdup to descend when using it for battery positive electrode active material. Consequently, battery behavior is deteriorated after the assembling.
The present inventors carry out the result that the method for sintering shrinkage conscientiously studies to suppressing grain growth, by be warming up to at least 100 ℃/minutes speed be higher than the temperature of sintering shrinkage initial temperature more than at least 100 ℃ that is recorded by heat engine tool testing machine (Thermo-mechanical analysis) till, keep after 1 minute～10 minutes, be cooled to aforementioned sintering shrinkage initial temperature with at least 100 ℃/minutes speed again, can suppress grain growth and carry out sintering shrinkage.
So-called sintering shrinkage initial temperature refers to the contraction initial temperature of trying to achieve with heat engine tool testing machine. Aforementioned maintenance temperature must be higher at least more than 100 ℃ than sintering shrinkage initial temperature. If keep temperature to be higher than 100 ℃ of sintering initial temperature less thaies, then because sintering shrinkage speed is slow, so sintering time need prolong. Grain growth consequently, the particle diameter of primary particle surpasses 0.5 μ m.
In the aforementioned sintering process, be higher than under the temperature of sintering shrinkage initial temperature more than at least 100 ℃, the particle diameter of primary particle is below 0.5 μ m more than the 0.2 μ m; And the retention time that obtains good battery behavior is at least more than 1 minute below 10 minutes. Because the retention time is less than 1 minute, heat transfer time is too short, if primary particle particle diameter less than 0.2 μ m, then crystallization is insufficient, and initial capacity diminishes. If the retention time surpasses 10 minutes, then owing to grain growth behind sintering shrinkage, so the primary particle particle diameter becomes greatly, the capacity dimension holdup descends.
Among the present invention, preferably 2 minutes～8 minutes retention time, more preferably 2 minutes～5 minutes.
Programming rate and cooling rate be defined as to the temperature range that keeps temperature at least 100 ℃/minutes and be because will shortly as much as possible suppress the growth of particle and only carry out sintering shrinkage by the retention time that makes the temperature range that particle grows up in the sintering initial temperature.
In addition, for the tap density that makes positive active material surpasses 2.2g/ml, the average void fraction of offspring is remained on below 10%, better be below 7%, is more preferably below 5%.
The crystallite dimension of aforementioned positive active material of the present invention is 400～960 dusts preferably. During crystallite dimension less than 400 dust, because crystallinity is insufficient, so the initial capacity of battery reduces, the capacity dimension holdup descends. In addition, if crystallite dimension surpasses 960 dusts, then the capacity dimension holdup sharply descends. So crystallite dimension is 500～920 dusts preferably, 700～920 dusts more preferably.
The lattice paprmeter of the positive active material of the Li-Mn system complex oxide with spinel structure of the present invention is more fortunately below 8.240 dusts. If lattice paprmeter surpasses 8.240 dusts, then the capacity dimension holdup of battery descends serious. Therefore, the better scope of lattice paprmeter is below 8.235 dusts, is more preferably below 8.233 dusts.
After the sinter that will have a Li-Mn system complex oxide of spinel structure is pulverized, (this particle is the offspring that is formed by the primary particle aggegation in the gained sized particles, it is following that its average grain diameter is preferably in 0.5 μ m) in add sintering accelerating auxiliaries (granulation promoter), the Li-Mn system complex oxide that granulation sintering after mixing and the granulation particle of the densification that obtains can be used as to have spinel structure is that the positive active material of the present invention of main body uses. The granulation particle of above-mentioned densification refers to tight or space particle seldom between the primary particle of its oxide. Positive active material of the present invention is the granulation particle of aforementioned densification, uses sintering accelerating auxiliaries described later to form.
Below, the preparation method of positive active material of the present invention is described.
Preparation method with Li-Mn system complex oxide of spinel structure is in atmosphere or in the oxygen flow, under 300～850 ℃ of temperature to the mixture of manganese compound and lithium compound or added the sintering that the mixture of the compound that contains the xenogenesis element that can replace manganese carries out more than 1 hour at least and form.
Crystallinity to Li-Mn system complex oxide with spinel structure is not particularly limited, even residual have unreacted lithium compound and Mn oxide also it doesn't matter. Use crystallinity high have the Li-Mn system complex oxide of spinel structure the time, though lattice paprmeter is not particularly limited, if adopt the positive active material of lattice paprmeter below 8.240 dusts, then can suppress the decline of capacity dimension holdup.
Raw material to Li-Mn system complex oxide with spinel structure is not particularly limited, and preferably known manganese compound for example, can use manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, hydrated manganese oxide, manganese carbonate and manganese nitrate etc. In addition, can use lithium hydroxide, lithium carbonate and lithium nitrate etc. as the lithiumation thing.
Situation is to adopt the good lithium compound of battery behavior reacts at low temperatures easily when can and be applicable to positive active material manganese carbonate as aforementioned manganese compound preferably.
Preparation manganese substituted type with Li1+xMn 2-x-yM yO 4The expression Li-Mn-M (xenogenesis element) system complex oxide the time, except the raw material of aforementioned manganese compound and lithium compound, also can use at least a kind of element that is selected from chromium, cobalt, aluminium, nickel, iron and the magnesium. Contain the xenogenesis element compound so long as by add any compound that thermal response can form aforesaid oxides all can, can add with lithium compound and manganese compound when adding thermal response aforementioned.
The method that cracks pulverizing to the offspring of aforementioned Li-Mn system complex oxide with spinel structure is not particularly limited, and can adopt known shredder and pulverizer. For example, media-agitation type pulverizer, ball mill, coating vibratory sieve, injector-type mill, tumbling mill etc. Cracking when pulverizing to adopt dry method also can adopt wet method. The solvent that can be used for wet method is not particularly limited, such as making water and alcohol etc.
Shrink to consider that from acceleration of sintering the granularity that cracks the Li-Mn system complex oxide with spinel structure after the pulverizing is extremely important.
Average grain diameter when granularity is measured with the Laser particle-size distribution analyzer better is below 5 μ m. Again good be do not contain particle diameter in the oversize grain more than the 5 μ m and average grain diameter below 2 μ m. Better be exactly not contain particle diameter to surpass the oversize grain of 3 μ m and average grain diameter below 1.5 μ m. Particularly preferred be average grain diameter more than 0.3 μ m below the 0.5 μ m, best is that average grain diameter is below 0.2 μ m.
To through cracking the Li-Mn system complex oxide particle of pulverizing and the mixed method of sintering accelerating auxiliaries is not particularly limited, for example, can use aforementioned media-agitation type pulverizer, ball mill, coating vibratory sieve and mixer etc. Hybrid mode can adopt any in dry method and the wet method. When cracking pulverizing Li-Mn system complex oxide, add the sintering accelerating auxiliaries, and mix simultaneously.
As long as sintering promotes that auxiliary agent can promote to be the sintering that the sized particles granulation is carried out that cracks with Li-Mn system complex oxide particle.Be preferably can fusion under the temperature below 900 ℃ compound, for example, fusible oxide maybe can become the precursor of oxide under 550 ℃～900 ℃ temperature, or with lithium or manganese solid solution or react and the oxide of fusion maybe can become the compound of oxide.
Sintering promotes auxiliary agent to comprise the compound of elements such as containing Bi, B, W, Mo and Pb, also these compounds at random can be used in combination.In addition, also can adopt by B 2O 3The compound or the MnF that combine with LiF 2The compound that combines with LiF.Wherein, well consider, be preferably the compound that contains Bi, B and W element from the sintering contractive effect.
The Bi compound comprises bismuth trioxide, bismuth nitrate, benzene first bromic acid bismuth, glycolic bismuth, bismuthyl carbonate and bismuth citrate and bismuth hydroxide etc.In addition, the B compound comprises diboron trioxide, boron carbide, boron nitride, boric acid etc.The W compound comprises tungsten dioxide and tungstic acid etc.
The addition that sintering promotes auxiliary agent converts corresponding in 1 mole of Mn in the Li-Mn system complex oxide, 0.0001～0.05 mole scope more fortunately by the metallic element that adds.If 0.0001 mole of the addition less than that converts by the metallic element that adds, then the sintering contractive effect is not good, if surpass 0.05 mole, then the initial capacity of active material diminishes.Therefore desirable addition is 0.005～0.03 mole.
Sintering promotes that auxiliary agent can also dissolve in the solvent with liquid use in Powdered use.During with Powdered interpolation, sintering promotes that the average grain diameter of auxiliary agent better is below 50 μ m, is more preferably below 10 μ m, is preferably in below the 3 μ m.Sintering promotes auxiliary agent to add before granulation/sintering, also can promote auxiliary agent that this auxiliary agent is immersed in granulation thing and carries out sintering at sintering after the granulation.
Sintering promotes that for example, used aforementioned sintering promotes that auxiliary agent remains in the positive active material and can predict by analysis in the manufacture method of the present invention in the cell positive material after auxiliary agent often remains in sintering.
Below, prilling process is described.
Prilling process comprises spray granulation, fluidized granulation method, compression comminution granulation and the stirring-granulating method etc. of having used aforementioned sintering to promote auxiliary agent.In addition, also can and use media flow seasoning and vibration of media seasoning etc.
As long as can form fine and close offspring of the present invention (comprising the granulation particle), its granulation formation method is not particularly limited.Stirring-granulating and compression granulation can improve the density of offspring, and the shape of the granulation particle that mist projection granulating makes is entirely sphere, all is good prilling process.The example of stirring-granulating device comprises the パ ウ レ ッ Network vertical granulating machine of Co., Ltd.'s system and only Pa Daer Co., Ltd. system drum-type disintegrating machine etc.The example of compression nodulizer comprises the system roller compaction machine MRCP-200 of this ironworker of grain Co., Ltd. type etc.The example of mist projection granulating device comprises ア シ ザ ワ ニ ロ ア ト マ イ ザ-Co., Ltd.'s system movable small spray dryer etc.
Size to the offspring of granulation is not particularly limited.If the average grain diameter through the offspring of granulation is excessive, then after the granulation immediately or crack pulverizing behind the sintering simply, the whole grain of classification obtains the granularity of wishing.Be preferably the offspring that average grain diameter is 10～20 μ m.
In order to improve granulation efficiency, also can add the granulation aid of organic system.
This granulation aid comprises copolymer, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, hydroxypropyl cellulose, methylcellulose, cornstarch, gelatin and the lignin etc. of acrylic resin, isobutene and maleic anhydride.
When adding granulation aid, can Powderedly adding, is good but add the granulation effect with the method for spraying behind the organic solvents such as water-soluble and alcohol.The addition of granulation aid promotes auxiliary agent corresponding to Li-Mn system complex oxide and the sintering that 100 mass parts have spinel structure, more fortunately below 5 mass parts, better below 2 mass parts.
Below, the sintering method through the offspring of granulation is described.
The degreasing method of the particle of process granulation is to keep 10 minute or more in atmosphere or in the oxygen flow, in 300～550 ℃ temperature range this particle.Be preferably in below 0.1% through the carbon residual quantity in the granulation thing of degreasing.
In order to suppress the particle growth sintering contraction is carried out, keep 1 minute or more in atmosphere or in the oxygen flow, in 550 ℃～900 ℃ temperature range the granulation particle after the degreasing, make sintering promote auxiliary agent to keep molten condition and carry out the sintering contraction, can realize the densification of offspring at Li-Mn system complex oxide particle surface.
Among the present invention, in order to suppress the particle growth sintering contraction is carried out, in atmosphere or in the oxygen flow with at least 100 ℃/minutes speed be warmed up to be higher than the sintering that records with the thermal mechanical performance test machine at least and shrink the temperature of 100 ℃ of initial temperatures till, keep after 1 minute～10 minutes, make temperature reduce to the sintering initial temperature with at least 100 ℃/minutes speed again, make it carry out sintering and shrink the densification that realizes offspring.Programming rate between room temperature and the sintering contraction initial temperature and cooling rate also can below 10 ℃/minute resembling in the past.
In addition, need not aforementioned organic system granulation aid carry out the sintering of granulation thing particle, similarly carry out sintering in atmosphere or in the oxygen flow atmosphere gas and shrink, also can realize the densification of offspring.
According to in the past the identical method of Li-Mn system complex oxide, positive active material of the present invention and the positive active material that made by manufacture method of the present invention are processed into lithium ion secondary battery anode, for the battery assessment.
Below, to the example of aforementioned positive active material of the present invention as the positive electrode use of non-aqueous secondary batteries described.
At first, conductive agent such as the aforementioned positive active material of mixed, carbon black or graphite and the solution that dissolved adhesives such as polyvinylidene fluoride (jointing material) are (for example according to the rules, N-methyl pyrrolidone etc.) obtain electrode paste, this electrode paste is coated on the collector body, and dry back makes positive electrode by pressurizations such as roll extrusion.Collector body can use known metallic collector bodies such as aluminium, stainless steel and titanium.
Electrolytic salt in the non-aqueous secondary batteries of the present invention in the used electrolyte can use fluorine-containing known lithium salts.For example, LiPF 6, LiBF 4, LiN (CF 3SO 2) 2, LiAsF 6, LiCF 3SO 3, LiC 4F 9SO 3Deng.The electrolyte of non-aqueous secondary batteries is for having dissolved at least a kind of electrolyte that is selected from the aforementioned fluorine-containing known lithium salts in nonaqueous electrolytic solution.The nonaqueous solvents of aforementioned nonaqueous electrolytic solution then can adopt chemistry and all more stable non-protonic solvent of chemical property.
For example, dimethyl carbonate, propylene carbonate, ethylene carbonate, carbonic acid methyl ethyl ester, carbonic acid methyl propyl ester, carbonic acid methyl isopropyl ester, carbonic acid methyl butyl ester, diethyl carbonate, carbonic acid ethyl propyl ester, carbonic acid diisopropyl ester, dibutyl carbonate, carbonic acid 1, carbonates such as 2-Aden ester, carbonic acid ethyl isopropyl ester, carbonic acid ethyl butyl ester.In addition, also comprise oligomeric ethers such as three ethanol methyl ethers, tetraethylene glycol dimethyl ether, aliphatic ester such as methyl propionate, methyl formate, aromatic series nitriles such as benzonitrile and tolyl nitrile, amide-types such as dimethyl formamide, sulfoxide classes such as dimethyl sulfoxide (DMSO), lactone such as gamma-butyrolacton, the sulfolane sulfides, N-vinyl pyrrolidone, phosphoric acid ester etc.Wherein, carbonates, aliphatic ester, ethers are good.
As the negative pole that uses in non-aqueous secondary batteries of the present invention, so long as reversibly the material of occlusion release lithium ion gets final product, there is no particular restriction.For example can use lithium metal, lithium alloy, carbon material (graphitiferous), metal chalcogen etc.
Below, the appraisal procedure of electrode characteristic is described.
According to 50: 34: 16 quality than mixed cathode active material, as the キ ャ ボ Off ト of electric conducting material system バ Le カ Application XC-72, as the tetrafluoroethylene resin of adhesive, with toluene with this mixture swelling 12 hours.To be coated on the collector body of making by the aluminium pressed metal, through the mixture of swelling with 2t/cm 2Exert pressure be shaped, make obtain after the toluene drying anodal.In addition, adopt the lithium paper tinsel as negative pole.
According to inferior propyl ester of 1: 2 volume ratio mixed carbonic acid and dimethyl carbonate, in this mixed liquor, dissolve LiPF then 6Make its concentration reach 1 mol, with this solution as electrolyte.In addition, adopt polypropylene system interlayer,, also can and be used as the silicon dioxide fibre filter paper (for example, ア De バ Application テ Off Network Toyo Co., Ltd. system QR-100) of reinforcing material in order to prevent to cause negative pole to generate the tiny short circuit of skeleton.Use above-mentioned positive pole, negative pole, electrolyte, interlayer and reinforcing material to make 2016 type button cells.In being set at 60 ℃ thermostat, temperature carries out 500 charge and discharge cycles tests.Condition determination is the discharge of rated current rated voltage charging-rated current, charging and discharge rate 1C (charging begins to end up being 2.5 hours to charging), and scanning voltage is 3.1V～4.3V.
The best mode that carries out an invention
Below, the present invention will be described to exemplify embodiment and comparative example, but the present invention is not limited to this.
The characteristic of positive active material is measured in accordance with the following methods shown in following example and table 1～3.
1) average grain diameter and specific area
The GRANULOMETER (HR850 type) that uses the production of CILAS Co., Ltd. is as the laser particle size analyzer, after with ultrasonic wave powder being dispersed in 0.2% aqueous solution of surfactant (flower king make De Moer (anion surfactant) P), measure particle size distribution.
2) tap density
Use Co., Ltd. to hide to hold scientific instrument and make institute's plain bumper (KRS-409 type), measure amplitude vibration with 8mm and knock tap density after 2000 times.
3) voidage
Mixed cathode active material and thermosetting resin, by solidifying the positive active material landfill is gone in the resin, after the slicing machine cut-out, mirror ultrafinish uses electronic scanner microscope (SEM) to take lapped face then.Measure the total sectional area A in the whole holes that comprise in the sectional area B of 1 offspring in the gained SEM photo and this offspring cross section with image analysis apparatus, calculate the voidage C (%) of 1 offspring with following formula, select the mean value of the voidage of 50 offsprings to be average void fraction randomly.
C(％)＝(A/B)×100
4) crystallite size
Adopt the Scherrer formula to calculate by the X-ray diffraction peak of (111) face that records under the following conditions.
That is, suppose that the crystallite profile does not possess cubical size distribution, the value that the diffraction beamwidth that uses the size according to crystallite to obtain is calculated by the half range value.In addition, behind tungsten carbide sample preparation product grinding mill pulverizing monocrystalline silicon, be external standard with the powder that sieves below the 44 μ m, device constant calibration curve draws.
[determinator and method]
Use the system Rad of Rigaku Denki Co., Ltd type goniometer to measure in the mode of METHOD FOR CONTINUOUS DETERMINATION, the RINT2000 series model application software of also using Rigaku Denki Co., Ltd is carried out the parsing of crystallite size as resolving software.
Condition determination is X ray (a CuK alpha ray), and power output is 50kV and 180mA, and gap width (3 place) is 1/2 °, 1/2 ° and 0.15mm, scan method is 2 θ/θ method, sweep speed is 1 °/minute, and measurement range (2 θ) is 17～20 °, is spaced apart 0.004 °.The precision of the crystallite size that is obtained by said method is ± 30 dusts.
5) lattice constant
By J.B.Nelson, the method for D.P.Rilkey (Proc.Phys.Soc., 57, 160 (1945)) try to achieve.
6) specific area
Measure with the BET method.
7) shape of granulation particle
Granulation particle photo with SEM shooting positive active material carries out image analysis then, tries to achieve circularity (circularity=4 π [area/(girth) of offspring 2]) and needle-like than (the absolute maximum length/across corner of needle-like ratio=pin).Each sample is measured 200 offsprings respectively, ask its mean value.
Embodiment 1
With ball mill mixing ratio surface area is 22m 2(Chuo Denki Kogyo Co., Ltd.'s system C2-10) and lithium carbonate (this village KCC system 3N), makes the atomic ratio of Li/Mn reach 0.51 composition to the manganese carbonate of/g.After in atmospheric atmosphere gas, being warming up to 650 ℃ from room temperature, kept 4 hours synthetic Li-Mn system complex oxide in this temperature with 200 ℃/hour firing rate.Except the Li-Mn system complex oxide, also detected the manganese sesquioxide managnic oxide of denier by X ray resolver (XRD) in this synthetic.The average grain diameter that records this synthetic with laser particle size measure of spread device is 10 μ m, and specific area is 7.7m 2/ g.
The Li-Mn system complex oxide with spinel structure of above acquisition is dispersed in the alcohol solvent, pulverizes with wet ball mill, making its average grain diameter is 0.5 μ m.Measurement result is, do not contain the macroparticle more than the 3 μ m in comminuted powder, and specific area is 27.8m 2/ g.In comminuted powder, add and sneak into the bismuth oxide that average grain diameter is 2 μ m, make the Bi/Mn atomic ratio reach 0.0026, then with the only Pa Daer system drum-type disintegrating machine RMO-6H of Co., Ltd. stirring-granulating.
In the mixed-powder of 100 mass parts Li-Mn system complex oxides and bismuth oxide, add being dissolved with the aqueous solution of 1.5 mass parts, carry out 16 minutes granulation as the polyvinyl alcohol of granulation aid.After cracking pulverizing gained granulation thing gently, making average grain diameter with the whole grain of air classifier is 15 μ m.The tap density of the granulation thing behind the whole grain is 1.65g/ml.
With gained granulation thing in atmosphere in 500 ℃ keep carrying out ungrease treatment (decomposition polyvinyl alcohol) in 2 hours after, the speed with 200 ℃/minute in atmosphere heats up, and keeps 20 hours at 750 ℃, obtains positive active material.Confirm to contain in the gained positive active material Bi element of a certain proportion of aforementioned bismuth oxide with ICP-AES method (inductance coupled plasma luminescence analysis).
The average void fraction of gained positive active material is 11.2%.In addition, the tap density of positive active material is 1.96g/ml, and crystallite size is 880 dusts, and lattice constant is 8.233 dusts.
According to following steps, make button cell with above positive active material.That is, according to 80: 10: 10 quality than mixed cathode active material, as the carbon black of electric conducting material, dissolved the N-N-methyl-2-2-pyrrolidone N-solution of polyvinylidene fluoride.Then, this mixed liquor is coated on the aluminium foil, makes positive pole after the pressurization.Negative pole uses the lithium paper tinsel with specific thickness.Used electrolyte is at inferior propyl ester and dimethyl carbonate and dissolve LiPE in the mixed solution that forms according to 1: 2 volume ratio mixed carbonic acid 6Back and the solution that obtains makes LiPE wherein 6Concentration reaches 1mol/l.Adopt above-mentioned positive pole, negative pole, polypropylene system interlayer, electrolyte and glass filter, make 2016 type button cells.
The charge and discharge cycles that the battery that makes in order to the top method is carried out 60 ℃ is tested.At charge-discharge velocity is that 1C (charging begins to end up being 2.5 hours to charging), voltage range are to carry out cycle charge-discharge 100 times under the condition of 3.0～4.2V.Capacity sustainment rate (%) and other measurement results after initial stage discharge capacity and 100 circulations are shown in table 1 in the lump.
Embodiment 2
Manganese raw material in Li-Mn system complex oxide synthesis condition is the electrolytic manganese dioxide, and other operations are all identical with embodiment 1, and carries out voidage, tap density, crystallite size, the lattice constant of offspring, the assessment of electrode characteristic.It the results are shown in table 1.
Embodiment 3
With ball mill mixed carbonic acid manganese, lithium carbonate and aluminium hydroxide, the atomic ratio that makes Li/Mn/Al is 1.02: 1.967: 0.013.Firing rate with 200 ℃/hour is warming up to 650 ℃ from room temperature in atmospheric atmosphere gas then, and it was kept 4 hours at 650 ℃, synthetic Li-Mn system complex oxide.Except the Li-Mn system complex oxide, also detected the manganese sesquioxide managnic oxide of denier with XRD in this synthetic.The average grain diameter of the synthetic that records with laser particle size measure of spread device is 10 μ m.
Pulverize gained Li-Mn system complex oxide, make its average grain diameter reach 0.5 μ m.Add boron oxide and granulation then therein, make the atomic ratio of B/Mn reach 0.0208.Then, except the granulation thing after the degreasing being carried out 0.5 hour the sintering at 750 ℃, other operations are all identical with embodiment 1.It the results are shown in table 1.
Embodiment 4
Except the atomic ratio of B/Mn is 0.009, granulation thing after the degreasing carries out 0.5 hour the sintering at 760 ℃, other operations are all identical with embodiment 3.It the results are shown in table 1.
Embodiment 5
Except the atomic ratio of B/Mn is 0.006, granulation thing after the degreasing carries out 0.5 hour the sintering at 770 ℃, other operations are all identical with embodiment 3.It the results are shown in table 1.
Embodiment 6
Granulation thing after degreasing carries out 20 hours the sintering at 760 ℃, and other operations are all identical with embodiment 1.It the results are shown in table 1.
Embodiment 7
Except using tungstic acid to replace bismuth oxide and add tungstic acid with 0.0208 W/Mn atomic ratio, and the granulation thing after the degreasing carries out outside 20 hours the sintering at 750 ℃, and other operations are all identical with embodiment 1.It the results are shown in table 1.
Embodiment 8
Firing rate with 200 ℃/hour in atmosphere makes Li-Mn system complex oxide synthetic among the embodiment 1 rise to 750 ℃ from room temperature, and keeps making in 20 hours its crystallization at 750 ℃.Then, except using the Li-Mn system complex oxide of above-mentioned crystallization, replace bismuth oxide and add boron oxide with 0.0208 B/Mn atomic ratio with boron oxide, and the granulation thing after the degreasing carries out outside 0.5 hour the sintering at 750 ℃, other operations are all identical with embodiment 1.It the results are shown in table 1.
Embodiment 9
Except the average grain diameter of the Li-Mn system complex oxide before the granulation is that 3.5 μ m, specific area are 10m 2Outside/the g, other operations are all identical with embodiment 3.It the results are shown in table 1.
Embodiment 10
Except using the synthetic Li-Mn system complex oxide by ball mill mixed carbonic acid manganese, lithium carbonate and aluminium hydroxide, and outside making wherein Li/Mn/Al atomic ratio reach 1.03: 1.967: 0.013 to form, other operations are all identical with embodiment 3.It the results are shown in table 1.
Table 1
Figure C0080995500191
Embodiment 11
Granulation thing after degreasing was 830 ℃ of sintering 20 hours, and other all carry out same operation with embodiment 1.It the results are shown in table 2.
Embodiment 12
Except using the synthetic Li-Mn system complex oxide by ball mill mixed carbonic acid manganese, lithium carbonate and aluminium hydroxide, and wherein Li/Mn/Al atomic ratio is reached outside 0.99: 1.967: 0.013 the composition, other all carry out same operation with embodiment 3.It the results are shown in table 2.
Embodiment 13
Make except carrying out whole grain that the average grain diameter of particle is the 65 μ m after the granulation, other all carry out same operation with embodiment 3.It the results are shown in table 2.
Embodiment 14
Except the atomic ratio of Bi/Mn is 0.0020 ratio, other all carry out same operation with embodiment 1.It the results are shown in table 2.Observe above positive active material with electronic scanner microscope (* 15,000 times), found that it is a round particle shown in Figure 1 through the whole grain of granulation sintering.The particle size distribution of this particle as shown in Figure 2.
Comparative example 1
The average grain diameter of the Li-Mn system complex oxide before granulation is the 6.0 μ m, and other all carry out same operation with embodiment 1.It the results are shown in table 2.
Comparative example 2
Mixing average grain diameter with ball mill is electrolytic manganese dioxide and the lithium carbonate of 20 μ m, makes the atomic ratio of Li/Mn reach 0.51.Then, the firing rate with 100 ℃/hour in atmosphere is warming up to 760 ℃, and keeps 24 hours in 760 ℃, synthetic positive active material.The gained positive active material is carried out similarly to Example 1 assessment, and it the results are shown in table 2.
Comparative example 3
Do not carry out the granulation except not adding sintering aids, other all carry out same operation with embodiment 1, and it the results are shown in table 2.
Comparative example 4
Except the granulation thing being carried out 20 hours the sintering at 750 ℃, other all carry out same operation with embodiment 3, and it the results are shown in table 2.
Table 2
Embodiment 15
With ball mill mixed carbonic acid manganese, lithium carbonate and aluminium hydroxide, make the atomic ratio of Li/Mn/Al reach 1.02: 1.967; 0.013 composition.Firing rate with 200 ℃/hour in atmospheric atmosphere gas is warming up to 650 ℃ from room temperature, and keeps 4 hours at 650 ℃, synthetic Li-Mn system complex oxide.Except the Li-Mn system complex oxide, also detected the manganese sesquioxide managnic oxide of denier by XRD in this synthetic.The average grain diameter that records this synthetic with laser particle size measure of spread device is 10 μ m.
Add boron oxide and make the atomic ratio of B/Mn reach 0.0208 in the Li-Mn of above acquisition system complex oxide, then it is dispersed in the alcohol solvent, pulverize with wet ball mill, making its average grain diameter is 0.3 μ m.Then, with the only Pa Daer system drum-type disintegrating machine RMO-6H of Co., Ltd. the gained comminuted powder is carried out stirring-granulating.
In the comminuted powder of 100 mass parts Li-Mn system complex oxides and boron oxide, add being dissolved with the aqueous solution of 1.5 mass parts, carry out 16 minutes granulation as the polyvinyl alcohol of granulation aid.After cracking pulverizing gained granulation thing gently, making average grain diameter with the whole grain of air classifier is 15 μ m.The tap density of the granulation thing behind the whole grain is 1.60g/ml.
Gained granulation thing is kept carrying out in 2 hours ungrease treatment (decomposition polyvinyl alcohol) in 500 ℃ in atmosphere.The sintering contraction initial temperature that records the prilling powder of process degreasing with hot mechanical test machine is 660 ℃.
Then, under the following conditions, above prilling powder through degreasing is carried out sintering processes with rotary kiln.
The soaking zone temperature of rotary kiln is 780 ℃, sets the feed speed of prilling powder, rotation number and the gradient of rotary kiln by the soaking zone for making through the prilling powder of degreasing in 3 minutes.Prilling powder begins from the input port to export 6.3 minutes altogether used time to entering the used time of soaking zone and coming out to rotary kiln from the soaking zone.
The average void fraction of gained positive active material is 2.1%.In addition, the average grain diameter 0.40 μ m of the major diameter of 500 primary particles that record by the SEM photo.
Identical with embodiment 1, make button cell with above-mentioned positive active material.
In 60 ℃ the battery that makes with said method is carried out the charge and discharge cycles test.At charge-discharge velocity is that 1C, voltage range are to carry out charge and discharge cycles repeatedly 100 times under the condition of 3.0～4.2V.
Table 3 has write down the capacity sustainment rate (%) after initial stage discharge capacity and 100 circulations.
Embodiment 16
Except the soaking zone temperature of rotary kiln is 780 ℃, to set outside the rotation number and gradient of feed speed, rotary kiln of prilling powder by the soaking zone in 9 minutes for making prilling powder through degreasing, other all carry out same operation with embodiment 15.It the results are shown in table 3.
Embodiment 17
Mixed carbonic acid manganese, lithium carbonate and vapor phase method aluminium oxide make the atomic ratio of Li/Mn/Al reach 1.02: 1.967: 0.013 composition.Firing rate with 200 ℃/hour in atmospheric atmosphere gas is warming up to 650 ℃ from room temperature, and keeps 4 hours at 650 ℃, synthetic Li-Mn system complex oxide.Except the Li-Mn system complex oxide, also detected the manganese sesquioxide managnic oxide of denier by XRD in this synthetic.The average grain diameter that records this synthetic with laser particle size measure of spread device is 10 μ m.
Add boron oxide and make the atomic ratio of B/Mn reach 0.0104 in the Li-Mn of above acquisition system complex oxide, then it is dispersed in the ion exchange water, pulverize with the media-agitation type atomizer, making its average grain diameter is 0.18 μ m.Then, adding corresponding to the Li-Mn system complex oxide in gained pulverizing slurry is the granulation aid (イ ソ バ Application 104, Kuraray Co., Ltd. system) of 1.5 quality %, carries out drying-granulating with the disc rotary type spray dryer.The granulation thing is the spherical particle of average grain diameter 18.3 μ m, and tap density is 1.54g/ml.
With gained granulation thing in atmosphere in 500 ℃ keep carrying out ungrease treatment in 2 hours after, under condition similarly to Example 15, carry out sintering with rotary kiln.
The average void fraction of gained positive active material is 1.7%, average grain diameter is that 0.27 μ m, tap density are 2.40g/ml, the specific area measured by the BET method is 0.8m 2/ g.Adopt method similarly to Example 15, the characteristic of the button cell that makes with above positive active material is as shown in table 3.
Embodiment 18
Except the temperature of rotary kiln soaking zone is 850 ℃, other all carry out same operation with embodiment 15.Its result is as shown in table 3.
Embodiment 19
Except the temperature of rotary kiln soaking zone is 850 ℃, other all carry out same operation with embodiment 17.Its result is as shown in table 3.
Comparative example 5
Except the temperature that makes the granulation thing after the degreasing with 10 ℃/minute speed is warming up to 750 ℃ from 650 ℃, and after keeping carrying out sintering in 0.5 hour, be cooled to outside 650 ℃ with 10 ℃/minute speed again, other all carry out same operation with embodiment 15.In addition, the gained positive active material is carried out similarly to Example 15 assessment.It the results are shown in table 3.
Comparative example 6
Except keeping carrying out the sintering in 20 hours at 750 ℃, other all carry out same operation with comparative example 5.It the results are shown in table 3.
Comparative example 7
Except the soaking zone temperature of rotary kiln is 780 ℃, in 0.5 minute, set the feed speed of prilling powder, the rotation number and the gradient of rotary kiln for making by the soaking zone through the prilling powder of degreasing, and prilling powder begins from the input port to export outside the used time amounts to 1.5 minutes to entering the used time of soaking zone and coming out to rotary kiln from the soaking zone, and other all carry out same operation with embodiment 15.It the results are shown in table 3.
Table 3
Embodiment 18 850 ℃ of 9 minutes 120 ℃ of/minute rotary kilns 1.4 2.51 2.66 0.3 8.237 0.73 1.29 128 86
Embodiment 19 850 ℃ of 9 minutes 120 ℃ of/minute rotary kilns 1.3 2.52 2.41 0.2 8.237 0.75 1.29 128 87
Comparative example 5 750 ℃ of 0.5 hour 10 ℃ of/minute box type furnaces 6.5 2.14 0.55 1.2 8.232 0.78 1.28 127 85
Comparative example 6 750 ℃ of 20 hours 10 ℃ of/minute box type furnaces 2.3 2.33 0.84 0.3 8.235 0.78 1.29 125 70
Comparative example 7 780 ℃ of 0.5 minute 120 ℃ of/minute rotary kilns 13.1 1.92 0.19 2.1 8.233 0.77 1.28 118 81
The measuring shape result of granulation particle resolves
Circularity (circularity=4 π [area/(girth) of the offspring that makes by table 1～3 illustrated embodiments 1～19 and comparative example 1～7 2]) and needle-like than the measurement result of (the absolute maximum length/width across corners of needle-like ratio=pin) can confirm positive active material that embodiment makes have circularity more than 0.7, needle-like is than in the feature below 1.35.
The possibility of utilizing on the industry
Positive active material of the present invention is compared with the in the past known offspring that utilizes cohesive force, in the difference of carrying out having aspect granulation and the sintering in essence. Compare with the positive active material that makes with conventional method, positive active material particle-dense of the present invention and be spherical, filling to electrode is good, even and also can show higher initial capacity and capacity dimension holdup when being used for secondary cell under hot environment.
Among the preparation method of positive active material of the present invention, by in the Li-Mn system complex oxide, adding the sintering accelerating auxiliaries of melting under the high temperature, not only can realize the densified of offspring, even the crystallite that causes because initial capacity and cycle characteristics are deteriorated that occurs when resembling with conventional method is grown up, also can obtain good battery performance. The excessive situation of grain growth that the primary particle size surpasses 0.5 μ m can appear in the offspring that conventional method makes when densified, thereby causes initial capacity and cycle characteristics deteriorated. But this problem can solve by the method for the present invention of the sintering accelerating auxiliaries of melting under the interpolation high temperature in the Li-Mn system complex oxide, obtains to have the positive active material of high filling and good battery performance.
Lithium rechargeable battery of the present invention is owing to having used the good positive active material of filling, so at high temperature also have good initial capacity and capacity dimension holdup.

Claims (22)

1. positive electrode active material for lithium ion secondary battery, described positive active material is characterized in that to have the Li-Mn system complex oxide particle of spinel structure, uses following formula:
Voidage (%)=(A/B) * 100 (1)
The voidage mean value of the aforementioned particles of expression is below 15%, and in the formula, A represents to be included in the total sectional area in 1 hole in the offspring cross section, and B represents the sectional area of 1 offspring.
2. positive electrode active material for lithium ion secondary battery as claimed in claim 1, wherein, aforementioned average void fraction is below 10%, and the average grain diameter of primary particle is 0.2～3 μ m.
3. positive electrode active material for lithium ion secondary battery as claimed in claim 1, wherein, the tap density of positive active material is more than 1.9g/ml.
4. positive electrode active material for lithium ion secondary battery as claimed in claim 3, wherein, the tap density of positive active material is more than 2.2g/ml.
5. positive electrode active material for lithium ion secondary battery as claimed in claim 1, wherein, the crystallite size of positive active material is 400～960 dusts.
6. positive electrode active material for lithium ion secondary battery as claimed in claim 1, wherein, the lattice constant of positive active material is below 8.240 dusts.
7. positive electrode active material for lithium ion secondary battery as claimed in claim 1, wherein, positive active material is to have the Li-Mn system complex oxide of spinel structure, described oxide maybe can become the element of oxide by the oxide of fusion under 550 ℃～900 ℃ temperature or contain the compound of this element or with lithium or manganese solid solution or react and the oxide of fusion maybe can become the element of oxide or the compound that contains this element is formed, the active material that obtains by granulation and sintering.
8. positive electrode active material for lithium ion secondary battery as claimed in claim 7, wherein, the oxide of fusion maybe can become the element of oxide or contain the compound of this element or with lithium or manganese solid solution or react and the oxide of fusion maybe can become the element of oxide or the compound that contains this element is selected from the element of Bi, B, W, Mo, Pb at least a kind or contain the compound of this element or by B under 550 ℃～900 ℃ temperature 2O 3With the compound of LiF composition or by MnF 2Compound with the LiF composition.
9. the preparation method of the described positive electrode active material for lithium ion secondary battery of claim 1, it is characterized in that, possess in the crushed material of Li-Mn system complex oxide and to add the oxide that is mixed into fusion under 550 ℃～900 ℃ temperature and maybe can become the element of oxide or contain the compound of this element or with lithium or manganese solid solution or react and the oxide of fusion maybe can become the element of oxide or contain the compound of this element, the step of carrying out granulation then with spinel structure.
10. the preparation method of positive electrode active material for lithium ion secondary battery as claimed in claim 9, its feature also is except granulation step, also to possess the step of aforementioned granulation thing being carried out sintering.
11. the preparation method of positive electrode active material for lithium ion secondary battery as claimed in claim 9, its feature also is, except granulation step, also possess and aforementioned granulation thing is shunk initial temperature from sintering the speed with at least 100 ℃/minutes heats up till the high temperature of this temperature more than at least 100 ℃ to being higher than, keep this temperature after 1 minute～10 minutes, make temperature reduce to the sintering initial temperature with at least 100 ℃/minutes speed again and carry out the step of sintering.
12. the preparation method of positive electrode active material for lithium ion secondary battery as claimed in claim 11, its feature also are, carry out sintering with rotary kiln.
13. the preparation method of positive electrode active material for lithium ion secondary battery as claimed in claim 10, its feature also is, when carrying out aforementioned sintering step, make at least a kind to be selected from the element of Bi, B, W, Mo, Pb or to contain the compound of this element or by B at Li-Mn system complex oxide particle surface 2O 3With the compound of LiF composition or by MnF 2The compound of forming with LiF carries out fusion and sintering.
14. the preparation method of positive electrode active material for lithium ion secondary battery as claimed in claim 9, its feature also be, the average grain diameter of crushed material of Li-Mn system complex oxide with spinel structure is below 5 μ m.
15. the preparation method of positive electrode active material for lithium ion secondary battery as claimed in claim 9, its feature also be, the average grain diameter of crushed material of Li-Mn system complex oxide with spinel structure is below 3 μ m.
16. the preparation method of positive electrode active material for lithium ion secondary battery as claimed in claim 9, its feature are that also aforementioned granulation step adopts spray granulation, stirring-granulating method, compression comminution granulation or fluidized granulation method to carry out.
17. the preparation method of positive electrode active material for lithium ion secondary battery as claimed in claim 9, its feature also is, in the aforementioned granulation step, adopt at least a kind of organic compound of the copolymer, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, hydroxypropyl cellulose, methylcellulose, cornstarch, gelatin and the lignin that are selected from acrylic resin, isobutene and maleic anhydride to use as granulation aid.
18. the preparation method of positive electrode active material for lithium ion secondary battery as claimed in claim 17, its feature also be, also possess in atmosphere or oxygen flow atmosphere gas in, the step of under 300 ℃～550 ℃ temperature, carrying out degreasing.
19. electrode paste wherein comprises the described positive electrode active material for lithium ion secondary battery of claim 1.
20. lithium ion secondary battery anode wherein comprises the described positive electrode active material for lithium ion secondary battery of claim 1.
21. lithium rechargeable battery wherein possesses the described lithium ion secondary battery anode of claim 20.
22. lithium rechargeable battery as claimed in claim 21, described secondary cell are button cell, winding type battery, cylinder battery, cubic type battery or laminate type battery.
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